EP0198719B1 - Procédé et appareillage de polymérisation de façon continue - Google Patents

Procédé et appareillage de polymérisation de façon continue Download PDF

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Publication number
EP0198719B1
EP0198719B1 EP86302853A EP86302853A EP0198719B1 EP 0198719 B1 EP0198719 B1 EP 0198719B1 EP 86302853 A EP86302853 A EP 86302853A EP 86302853 A EP86302853 A EP 86302853A EP 0198719 B1 EP0198719 B1 EP 0198719B1
Authority
EP
European Patent Office
Prior art keywords
paddles
reactor
polymerization
barrel
shafts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86302853A
Other languages
German (de)
English (en)
Other versions
EP0198719A3 (en
EP0198719A2 (fr
Inventor
Masami Yamawaki
Shuichi Chino
Minamisawa-Tsuyoshi
Masaaki Nakamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polyplastics Co Ltd
Original Assignee
Polyplastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co Ltd filed Critical Polyplastics Co Ltd
Publication of EP0198719A2 publication Critical patent/EP0198719A2/fr
Publication of EP0198719A3 publication Critical patent/EP0198719A3/en
Application granted granted Critical
Publication of EP0198719B1 publication Critical patent/EP0198719B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/182—Details relating to the spatial orientation of the reactor horizontal

Definitions

  • the present invention relates to a method of and apparatus for continuously producing a polymerization product in fine particle form from a substantially liquid-form feedstock.
  • the invention relates to continuously producing a solid polymerization product in fine particle form from a liquid feedstock in a so-called continuous agitator-mixer type polymerization reactor including two parallel shafts which are rotated in the same or in opposite directions, a multiplicity of paddles mounted on each of the shafts, and a barrel with its inner periphery proximate to the outer peripheries of the rotated paddles.
  • the continuous polymerization utilizing a twin shaft apparatus of the kind above referred to is characterised in that the rear-end of the reactor which includes an outlet port is raised so that the major axis of the reactor and in particular, the rotational axes of the shafts and paddles of the reactor, have a slope angle of 1-10 0 relative to the horizontal upwardly towards the outlet end. Reaction takes place in the reactor as installed in such inclined state.
  • the invention extends to the apparatus and to the method for performing this polymerization.
  • the invention relates to a system of the latter case.
  • a typical example of continuous manufacture of a solid polymerization product through such polymerization reaction as involved in the latter case is polyvinyl chloride production through bulk polymerization, and another is polyacetal resin production through bulk polymerization.
  • a method of manufacturing polyacetal resin is mainly taken up.
  • reaction is so fast that the phase change is very abrupt; hence, it is no easy task to control the reaction.
  • a large bulky and tough product is produced in an instantaneously short time, so that material handling in the subsequent crushing, cleaning, and refining stages is extremely difficult.
  • temperature control is almost impossible, with the result of quality deterioration and unfavorable rate of conversion.
  • the former type is claimed as having good self-cleaning characteristics; and in the area of the latter type, there has been proposed an arrangement such that shear force is variably effected automatically in a desired direction according to the phase change, as disclosed in Japanese Published Unexamined Patent Application.
  • manufacturing techniques employed for industrial production of polyacetal resin are largely based on said proposal.
  • the present inventors directed their research efforts toward improving the operating characteristics of a parallel two-shaft agitator-mixer type polymerization reactor and achieving efficient production of polymerization products in fine particle form, and as a result they arrived at the present invention.
  • the invention provides agitator-reactor apparatus for continuously producing a polymerization product from a liquid feedstock, the apparatus being of the kind having twin parallel rotating or contra-rotating shafts each equipped with paddles and enclosed within a barrel, and with an inlet and an outlet at each respective end of the barrel, characterised in that the apparatus is arranged such that the axes of the shafts are inclined at an angle of 1°-10° to the horizontal upwardly towards the outlet end of the barrel.
  • the paddles as they rotate are closely confined by the walls of the barrel, the barrel sloping upwardly towards its outlet end at the same angle to the horizontal as is made by the axes of the rotating shafts.
  • the said angle is preferably 1° to 5°.
  • the preferred disposition of the said paddles is in corresponding pairs on the two shafts, wherein the paddles of at least one of said corresponding pairs of paddles are shaped to tend to promote the flow of the material being processed towards the outlet.
  • the paddles of at least one other of said corresponding pairs of paddles are preferably shaped so as to tend to reverse the flow of material being processed.
  • each paddle When viewed along the axis of rotation of its shaft, each paddle preferably has a major axis and a minor axis, with the corresponding paddle of the pair being similarly shaped such that as the paddles rotate the outer peripheries of the paddles of the corresponding pair are maintained close to one another.
  • the invention also provides a method of continuous polymerization for continuously producing a solid polymerization product from a liquid feedstock by employing agitator-reactor apparatus which includes two parallel shafts rotatable in the same or in opposite directions, a multiplicity of paddles mounted on each of the shafts, each paddle, when viewed along the axis of rotation of the shafts, having a major and a minor axis and a barrel with its inner periphery proximate to the outer peripheries of the paddles, said paddles being arranged so that as the paddles rotate their extremities are maintained close to one another, said reactor being such that feedstock is charged from an inlet port provided at one end of the reactor and the polymerization product is discharged from an outlet port provided at the other end, wherein the outlet end of the reactor including the outlet port is raised so that the major axis of the reactor has a slope angle of 1°-10°, and preferably not more than 5°, relative to the horizontal and upwardly towards the reactor outlet end, and wherein the reaction takes place
  • slope angle is less than 1°, no sufficient advantage of the invention may be obtained. If the slope angle is more than 10°, the mechanism which supports the rotatable shafts and provides rotational power is subject to considerable load, so that troubles may be encountered during any prolonged operation; and difficulties may also arise in conjunction with hermetic maintenance of gland seals. Such a high slope angle is therefore not practical. In order to obtain good operating efficiency and to take good advantage of the invention, a preferred range of slope angles is 1-5°.
  • any known type of paddle may be used without particular limitation.
  • Figure 3(1), (2) and (3) shows several sectional paddle configurations within a barrel body 8 (sections perpendicular to the agitator shafts 9).
  • Various types of paddles 10,-such as so-called convex lens-type, elipsoid-type, and quasi-triangle, or those types provided at front end with some notch or saw-tooth feature for scraper effect, may be employed according to the circumstance or condition involved. It is also possible to use eccentric disc type or eccentrically transformed disc type paddles. In effect, these types of paddles may be suitably selected and suitably arranged in combination according to the polymerization condition or aspect involved. Rather, one feature of the invention lies in the fact that such suitable combinations can be broadly selected.
  • UD (where L is the length of the reactor, and D is the inner diameter thereof) should normally be less than 20, or preferably less than 15. On the other hand, if sufficient conversion is to be attained, UD should preferably be more than 5.
  • the rotational speed of the agitator shafts should be within the range of 0.1-1.0 m/sec in terms of peripheral speed at the front edge of the paddle. In the method of the invention, however, the desired product can be effectively obtained even if the speed is less than 0.1 m/sec.
  • two cases may be considered, i.e., rotation in same direction and rotation in opposite directions, as earlier mentioned; and the invention may be equally applied in either case.
  • the invention relates to a polymerization method for producing a solid polymerization product from a liquid stock, or in other words, a polymerization method of such system that the polymeric masses are insoluble in the material monomers and that a completely solid polymerization product is separated out as polymerization progresses.
  • the method of the invention can be widely applied. More preferably, the method is employed for the purpose of polymerizing vinyl chloride, or homopolymerizing or copolymerizing trioxane.
  • trioxane copolymerizing there is no particular limitation as to copolymerizable monomers in a system wherein trioxane is contained as a principal ingredient in an amount of more than 50 mol%.
  • the polymerizing catalyst to be used. Needless to say, a small amount of anhydrous inert solvent or molecular-weight regulator, or other additive may be effectively used.
  • the method of the invention employs such reactor installed with a suitable slope angle to the horizon.
  • the mechanical arrangement employed in the invention may be similar to the one conventionally employed; however, the arrangement is advantageous in that it permits the fill rate of reactor contents to be readily kept constant in the direction of the major axis, in that the fill rate level can be readily adjusted, and in that any abrupt phase change or volumetric change can be readily relaxed, there being no possibility of substantial fluctuation in agitation efficiency.
  • the invention is based on a novel and unique concept as evidenced by these incredibly good improvements in reactor functions.
  • continuous polymerization reaction can be steadily carried out even where a large-scale reactor is employed, and thus polymerization products of good and uniform quality can be obtained in the form of particle mass of a desired configuration and size and at a high yield.
  • numeral 1 is a stock inlet port
  • 2 is a product outlet port
  • 3 is a barrel body
  • 4 is a polymerizing catalyst inlet port
  • 5 and 5' are bearings for the two shafts.
  • Numeral 6 is a jacket surrounding the outer periphery of the barrel and divided into three sections. Shown by 7 are thermocouples mounted at temperature measuring junctions 1-6. (There is no limitation as to the number and locations of thermocouples.) It is noted that 8 denotes an angle which the axis makes with the horizontal.
  • Fig. 2 is a schematic illustration of types of paddles and one example of their arrangement corresponding to Fig. 1; in the figure, each rectangle expresses a pair of paddles having a convex lens-like section without twist, and each rectangle with an oblique line denotes a pair of forward feed paddles (shown by ISJ) or a pair of backward feed paddles (shown by Z), as the case may be. Numerals at the bottom denote numbers of paddles counted from the inlet port.
  • a feedstock consisting of trioxane monomers mixed with 2.5% of ethylene oxide and 500 ppm of methylal as a regulator was introduced through the inlet port at a per-hour rate of 10 parts by weight, and a polymerizing catalyst consisting of a cyclohexane solution of boron trifluoride and dibutyl etherate was introduced through the catalyst inlet port 4 at a rate equivalent to 34 ppm relative to the polymerizable monomers.
  • Oil heated to 90°C was circulated through the jacket 6 for heating the reactor, and the rotational speed of the two shafts was maintained at 50 rpm.
  • Polymerization products as discharged from the outlet port 2 were sampled from time to time for measurement of their detention time, discharge rate, degree of conversion, and polymerization product melt index (MI). Variations in the measurements were examined. Also, internal temperature changes were recorded.
  • MI polymerization product melt index
  • the polymerization product was of a fine particle size of the order of less than 2 mm dia., with a minor proportion of particles of not more than 3 mm dia.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Claims (8)

1. Appareil agitateur-réacteur pour la production continue d'un produit de polymérisation à partir d'une charge d'alimentation liquide, l'appareil étant du type comportant deux arbres parallèles rotatifs tournant dans le même sens ou en sens contraires équipés chacun de palettes et enfermés dans un fourreau, une entrée et une sortie étant présentes aux extrémités respectives du fourreau, caractérisé en ce que l'appareil est agencé de telle manière que les axes des arbres sont inclinés à un angle de 1 à 10° par rapport à l'horizontale en s'élevant vers l'extrémité de sortie du fourreau.
2. Appareil selon la revendication 1, dans lequel les palettes lorsqu'elles tournent sont étroitement ajustées aux parois du fourreau, le fourreau étant incliné en s'élevant vers son extrémité de sortie avec le même angle que celui formé par les axes des arbres rotatifs.
3. Appareil selon la revendication 2, dans lequel ledit angle est de 1° à 5°.
4. Appareil selon l'une quelconque des revendications 1 à 3, dans lequel lesdites palettes sont disposées par paires de palettes correspondantes sur les deux arbres, et dans lequel les palettes d'au moins l'une desdites paires de palettes correspondantes sont conformées pour avoir tendance à favoriser l'écoulement de la matière en cours de traitement vers la sortie.
5. Appareil selon la revendication 4, dans lequel les palettes d'au moins une autre desdites paires de palettes correspondantes sont conformées pour avoir tendance à inverser l'écoulement de la matière en cours de traitement.
6. Appareil selon l'une quelconque des revendications 1 à 5 précédentes, dans lequel chaque palette, observée suivant l'axe de rotation de son arbre, présente un grand axe et un petit axe, la palette correspondante de la paire étant semblablement conformée, et dans lequel, lorsque les palettes tournent, les périphéries extérieures des palettes de la paire de palettes correspondantes restent proches l'une de l'autre.
7. Un procédé de polymérisation continue pour produire en continu un produit de polymérisation solide à partir d'une charge d'alimentation liquide en utilisant un appareil agitateur-réacteur selon l'une quelconque des revendications 1 à 6.
8. Un procédé de polymérisation continue tel que spécifié dans la revendication 7, dans lequel la charge liquide est du trioxanne ou un liquide mixte composé de trioxanne comme ingrédient principal et d'un comonomère qui est copolymérisable avec lui, et dans lequel le produit de polymérisation solide est un polymère de trioxanne ou un copolymère de trioxanne.
EP86302853A 1985-04-17 1986-04-16 Procédé et appareillage de polymérisation de façon continue Expired - Lifetime EP0198719B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60081697A JPS61238812A (ja) 1985-04-17 1985-04-17 トリオキサンの連続重合方法
JP81697/85 1985-04-17

Publications (3)

Publication Number Publication Date
EP0198719A2 EP0198719A2 (fr) 1986-10-22
EP0198719A3 EP0198719A3 (en) 1988-05-04
EP0198719B1 true EP0198719B1 (fr) 1990-08-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86302853A Expired - Lifetime EP0198719B1 (fr) 1985-04-17 1986-04-16 Procédé et appareillage de polymérisation de façon continue

Country Status (6)

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US (1) US4661570A (fr)
EP (1) EP0198719B1 (fr)
JP (1) JPS61238812A (fr)
KR (1) KR920001666B1 (fr)
CA (1) CA1265287A (fr)
DE (1) DE3673682D1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2735596B2 (ja) * 1989-01-20 1998-04-02 出光石油化学株式会社 スチレン系重合体の製造方法
CN1080731C (zh) * 1994-10-27 2002-03-13 旭化成株式会社 聚甲醛生产方法
KR100508905B1 (ko) * 2002-11-11 2005-08-17 주식회사 엘지화학 스티렌계 중합체 제조용 반응기
KR100508904B1 (ko) * 2002-11-19 2005-08-17 주식회사 엘지화학 중합체 제조 시스템
JP6282805B2 (ja) * 2013-04-25 2018-02-21 ポリプラスチックス株式会社 ポリアセタール共重合体の製造方法
JP6022993B2 (ja) * 2013-04-25 2016-11-09 ポリプラスチックス株式会社 ポリアセタール共重合体の製造方法
CN103406087A (zh) * 2013-08-27 2013-11-27 北京化工大学 一种节能高效自清洁聚合工艺及装置
JP5814414B2 (ja) * 2014-03-31 2015-11-17 ポリプラスチックス株式会社 ポリアセタール共重合体の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1257780A (fr) * 1960-02-26 1961-04-07 Saint Gobain Perfectionnement à la polymérisation en masse de dérivés de l'éthylène
DE1432024A1 (de) * 1961-04-18 1969-08-07 Aachener Misch & Knetmasch Mischmaschine
JPS57101A (en) * 1980-06-04 1982-01-05 Mitsui Petrochem Ind Ltd Method and apparatus for polymerization
JPS5740520A (en) * 1980-08-22 1982-03-06 Polyplastics Co Continuous polymerization
JPS5832619A (ja) * 1981-08-19 1983-02-25 Asahi Chem Ind Co Ltd ポリオキシメチレンの製造方法

Also Published As

Publication number Publication date
US4661570A (en) 1987-04-28
EP0198719A3 (en) 1988-05-04
CA1265287A (fr) 1990-01-30
KR860008211A (ko) 1986-11-14
DE3673682D1 (de) 1990-10-04
EP0198719A2 (fr) 1986-10-22
KR920001666B1 (ko) 1992-02-22
JPH058725B2 (fr) 1993-02-03
JPS61238812A (ja) 1986-10-24

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